1,5-diphenylpyrazole-3-carboxylic acid derivatives for the protection of cultivated plants

ABSTRACT

1,5-diphenylpyrazole-3-carboxylic acid derivatives of the formula ##STR1## are capable of antagonising specifically the phytotoxic action of phenoxypropionic acid ester herbicides of the formula II ##STR2## in which G represents ##STR3## Compositions, containing those compositions, as selective herbicides and the use of those two active ingredients for controlling weeds in crops of useful plants are described, as are also novel 1,5-diphenylpyrazole-3-carboxylic acid derivatives corresponding to the formula I and the preparation thereof.

The present invention relates to novel 1,5-diphenylpyrazole-3-carboxylicacid derivatives and to the use thereof for the protection of cultivatedplants against the harmful effect of herbicidally activephenoxyalkanecarboxylic acid esters, and to herbicidal compositionscontaining these 1,5-diphenylpyrazole-3-carboxylic acid derivatives or acombination of a herbicide and a 1,5-diphenyl-3-pyrazolecarboxylic acidderivative as antagonist. The invention relates also to the novel1,5-diphenylpyrazole-3-carboxylic acid derivatives and to thepreparation thereof.

When using phenoxyalkanecarboxylic acid herbicides, such as, forexample, phenoxyphenoxy- and pyridyloxyphenoxy-propionic acidderivatives, the cultivated plants can be considerably damaged,depending on factors, such as, for example, the amount of herbicide andthe method of application, the type of cultivated plant, soil conditionand climatic conditions, such as, for example, hours of daylight,temperature and amounts of rainfall. Severe damage may occur especiallywhen, within the framework of the crop rotation, cultivated plants thatare resistant to the herbicides are to be followed by other cultivatedplants that have no, or only insufficient, resistance to the herbicides.

It has surprisingly now been found that it is possible to protectcultivated plants against damage caused by herbicidally activephenoxypriopionic acid derivatives by treating the cultivated plants,parts of those plants or land intended for growing the cultivated plantswith a safener selected from a group of1,5-diphenylpyrazole-3-carboxylic acid derivatives. The herbicidalaction against weeds and weed grasses is not cancelled by thosederivatives.

1,5-diphenylpyrazole-3-carboxylic acid derivatives that are suitable forthe protection of cultivated plants from the harmful effects ofherbicidally active phenoxyphenyoxy-, pyridin-2-yloxyphenoxyl-,benzoxazolyloxyphenoxy-, benzothiazolyloxyphenoxy- orquinoxalinyloxyphenoxy-propionic acid derivatives, correspond to theformula I ##STR4## in which each of R₁ and R_(b), independently of theother, represents halogen, C₁ -C₅ -alkyl, C₁ -C₅ -haloalkyl, C₂ -C₅-alkenyl, C₂ -C₅ -alkynyl or cyano, n represents zero or an integer from1 to 3 and the group --OR₁ represents hydroxy, a salt radical or anydesired ester radical.

In the radical --OR₁ : R₁ represents especially hydrogen, aplant-physiologically tolerable metal or ammonium cation, a C₁ -C₁₈-alkyl or C₃ -C₁₈ -cycloalkyl radical that is unsubstituted or mono- orpolysubstituted by C₂ -C₈ -alkenyl, C₂ -C₈ alkynyl, C₃ -C₈-cycloalkenyl, n cyan or by an --XR₁₀, --CXR₁₀, --CX--XR₁₀, --CXNR₃ R₄,--XCXR₁₀, --XCXNR₃ R₄, --NR₃ R₄, --NR₃ CONR₃ R₄, --CONR₃ --NR₃ R₄,--CONR₃ --NR₃ COR₄, --Si(C₁ -C₄ alkyl)₃, --C(OR₇)(OR₈)OR₉ or PO(R₅)R₆radical; a heterocycle Q that is bonded via C or N; an unsubstituted orsubstituted phenyl or naphthyl radical U, a radical E-U or an imidoradical --N═C(R₂)R₂, R₂ represents especially C₁ -C₄ -alkyl or C₃ -C₇-cycloalkyl, or the two radicals R₂ together represent especially a 4-to 6-membered C₄ -C₁₂ -alkylene radical that may be branched and/orinterrupted by oxygen or sulphur, each of R₃ and R₄, independently ofthe other, represents especially hydrogen, or C₁ -C₈ -alkyl or C₃ -C₈-cycloalkyl each of which is unsubstituted or substituted by C₂ -C₆-alkenyl, C₂ -C₆ -alkynyl, C₃ -C₇ -cycloalkyl, halogen, C₁ -C₈ -alkoxy,C₂ -C₈ -alkoxyalkoxy, C₁ -C₈ -alkythio or by cyano, and one of R₃ and R₄alternatively represents C₁ -C₈ -alkoxy, --COOR₁₀, --CONH₂, CONH(C₁ -C₄-alkyl), CON(R₂)R₂, --NH₂, --NH (C₁ -C₂ alkyl)--N(R₂)R₂, a heterocycleQ, or a phenyl or naphthyl radical U that is bonded to the nitrogen atomdirectly or via a C₁ -C₁₄ -alkylene bridge, R₃ and R₄ together representespecially a 4- to 6-membered C₄ -C₁₂ -alkylene or -alkenylene chainthat may branched and/or interrupted by oxygen, sulphur, N (C₄ -C₄-alkyl), N(benzyl), --SO₂ --, --CO-- or by --C(OR₇)OR₈, and that may besubstituted by halogen, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, --NH₂, --NH (C₁-C₄ -alkyl) or by --N(C₁ -C₄ -alkyl)₂, each of R₅ and R₆, independentlyof the other, represents especiall C₁ -C₄ -alkyl, hydroxy or C₁ -C₄-alkoxy, each of R₇ and R₈, independently of the other, representsespecially C₁ -C₄ -alkyl, R₇ and R₈ together represent especially C₂ -C₄-alkylene, each of R₉ and R₁₀, independently of the other, representsespecially hydrogen, or C₁ -C₈ -alkyl or C₃ -C₈ -cycloalkyl each ofwhich is unsubstituted or substituted by C₂ -C₆ -alkenyl, C₂ -C₆-alkynyl, C₃ -C₆ -cycloalkenyl, halogen, C₁ -C₄ -alkoxy, C₂ -C₈-alkoxyalkoxy, C₁ -C₆ -alkoxycarbonyl, C₁ -C₆ -haloalkoxycarbonyl, aheterocycle Q or by a phenyl or naphthyl radical U, R₉ and R₁₀ alsorepresent especially the phenyl or naphthyl radical U, or a heterocycleQ bonded via C, Q represents especially a saturated or unsaturated 5- to12-membered heterocycle that contains from 1 to 4 hetero atoms N, O or Sor a --SO--, --SO₂ --, N(C₁ -C₄ -allyl) or N(benzyl) group and that maybe substituted by halogen, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄-haloalkyl, C₁ -C₄ -haloalkoxy, cyano or by nitro, E representsespecially a C₁ -C₄ -alkylene bridge, a C₃ -C₄ -alkenylene bridge or aC₃ -C₄ -alkynylene bridge, U represents especially a phenyl or naphthylradical that is unsubstituted or mono- or poly-substituted by halogen,C₁ -C₄ -alkyl, C₁ -C₄ -alkyl, C₁ -C₄ -alkylsulphinyl, C₁ -C₄-alkylsulphonyl, C₁ -C₄ -haloalkyl, C₁ -C₄ -haloalkoxy, cyano, nitro,--COOH, --COOC₁ -C₄ -alkyl, --COC₁ -C₄ -alkyl, CONH₂, CONH(C₁ -C₄-alkyl), CON(C₁ -C₄ -alkyl)₂, --SO₂ NH₂, SO₂ NH(C₁ -C₄ -alkyl), SO₂ N(C₁-C₄ -alkyl), pyrrolidino, piperidino or by the pyrrolidinocarbonyl,piperidinocarbonyl or morpholinocarbonyl radical, and X representsespecially oxygen or sulphur.

Plant-physiologically tolerable metal and ammonium cations should beunderstood as meaning the cations of salts customarily used inherbicides, such as alkali metal, alkaline earth metal, iron, copper,manganese or ammonium-alkylammonium, hydroxyalkylammonium oralkoxyalkylammonium cations.

Alkyl radicals should be understood as meaning radicals having thespecified number of carbon atoms. These radicals may be straight-chainedor branched. The most usual radicals are, for example, methyl, ethyl,n-propyl, isopropyl, n-butyl, isobutyl, sec.-butyl, tert.-butyl,n-pentyl, isopentyl, n-hexyl and n-octyl. The alkenyl and alkynylradicals may also be straight-chained or branched and they contain from3 to 6 carbon atoms. The most common radicals are, for example, allyl,methallyl, butene, butadiene, propynyl, methylpropynyl, 1-butynyl and2-butynyl. Cycloalkyl or cycloalkenyl radicals have preferably from 3 to12 carbon atoms and may also be benzo-fused. Typical representativesare, for example, cyclopropyl, cyclopentyl, cyclohexyl, cyclohexenyl,indan, tetrahydronaphthalene and Decalin. Halogen should be understoodas meaning fluorine, chlorine, bromine or iodine, especially fluorine orchlorine. Haloalkyl and haloalkenyl radicals may be mono- orpoly-substituted by halogen.

The radical Q is a saturated or unsaturated 5- to 12-memberedheterocycle which may also contain one, two or three further heteroatoms or a sulphinyl or sulphonyl group, may be interrupted by one ortwo carbonyl groups and which may be benzo-fused, unsubstituted orsubstituted.

Suitable hetero atoms are one, two or three further nitrogen atoms andup to two sulphur or oxygen atoms, although 2 oxygen atoms may not bedirectly vicinal.

Examples of such heterocycles are given below: pyrroline, pyrrolidine,imidazoline, imidazolidine, pyrazoline, pyrazolidine, isoxazoline,isoxazolidine, oxazoline, oxazolidine, isothiazolidine, thiazolines,thiazolidines, dithiazolidines, oxadiazolidines, pyridine, piperidine,piperazine, tetrahydro-pyrimidine and -pyrazine, pyrimidine, pyridazine,morpholine, thiomorpholine, thiazines, hexahydrotriazines,tetrahydrotriazines, oxadiazines, oxatriazines, hexahydroazepine,hexahydrodiazepines, diazepines, hexahydrooxazepines, azacyclooctane,benzofuran, benzothiophene, indole, indoline, isoindoline,benzimidazoline, benzindazoline, benzoxazoline, benzothiazolines,benzisoxazoline, benzotriazole, quinoline, tetrahydroquinoline,tetrahydroisoquinoline, quinazoline, quinoxaline, phthalazine,benzomorpholine, benzothiomorpholine, tetrahydrobenz-azepines and-diazepines, tetrahydrobenzoxazepines, 1,5-diazabicyclo[4.3.0]nonanes,dihydrobenzoxazines, 1,6-diazabicyclo[5.3.0]decanes,1,4-diazabicyclo[3.3.0]-octanes and 1,5-diazabicyclo[4.4.0]decanes.

The above-mentioned heterocycles may also be substituents. Furtherexamples of heterocyclic systems having a substituent function are, forexample, pyrrole, imidazole, pyrazole, isoxazole, oxazole, isothiazole,thiazole, triazoles, oxadiazoles, thiadiazoles, tetrazoles,oxatriazoles, thiatriazoles, furan, tetrahydrofuran, dioxoles,dioxolanes, oxathiols, oxathiolanes, thiophene, tetrahydrothiophene,dithiolanes, dithiazoles, pyridine, pyrans, thiopyrans, pyridazine,pyrimidine, pyrazine, tetrahydropyran, tetrahydrothiopyran, dioxines,dioxans, dithiins, dithianes, oxazines, thiazines, oxathiins,oxathianes, triazines, oxadiazines, thiadiazines, oxathiazines,dioxazines, azepines, oxepins, thiepines, diazepines, oxazepins,indoles, benzofurans, benzothiophenes, indazoles, benzimidazoles,benzodioxoles, benzodithiols, benzisoxazoles, benzothiazoles,benzoxazoles, benzoxathiols, benzotriazoles, benzoxadiazoles,benzofurazan, benzothiadiazoles, quinoline, isoquinoline, chromenes,chroman, isochromene, isochroman, thiochromenes, isothiochromenes,thiochroman, isothiochroman, cinnoline, quinazoline, quinoxaline,phthalazine, benzodioxines, benzodithiins, benzoxazines, benzodioxans,benzoxathianes, benzotriazines, benzazepines, benzodiazepines,benzoxazepines, purines, pteridines, phenoxazines and phenothiazines.

The heterocyclic radicals may be substituted by halogen C₁ -C₄ -alkyl,C₁ -C₄ -alkoxy, C₁ -C₄ -haloalkyl, C₁ -C₄ -haloalkoxy, cyano or bynitro.

The pyrazole derivatives of the formula I have an outstanding ability toprotect cultivated plants against the harmful effect of herbicidallyactive 2-[4-(phenoxy, pyridin-2-yloxy, benzoxazolyloxy,benzothiazolyloxy and quinoxalin-2-yloxy)-phenoxy]-propionic acid estersof the formula II ##STR5## in which G represents ##STR6## in which Hal₁represents fluorine, chlorine, bromine, iodine or trifluoromethyl, Hal₂represents hydrogen, fluorine, chlorine, bromine or trifluoromethyl, Zrepresents nitrogen or methine --CH═, X represents an oxygen or sulphuratom, R₁ represents halogen, trifluoromethyl, nitro, cyano, C₁ -C₄-alkyl or C₁ -C₄ -alkoxy and n represents 0, 1, 2 or 3.

In the compounds of the formula II, halogen represents fluorine,chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.##STR7## in which each of R₁₁ and R₁₂, independently of the other,represents hydrogen, C₁ -C₈ -alkoxy, C₁ -C₈ -alkyl, phenyl or benzyl,and R₁₁ and R₁₂ together with the nitrogen atom carrying them representa 5- or 6-membered saturated nitrogen heterocycle that may beinterrupted by an oxygen or sulphur atom,

R₁₃ represents C₁ -C₄ -alkyl, C₃ -C₄ -alkenyl, C₃ -C₄ -alkynyl or C₂ -C₄-alkoxyalkyl,

R₁₄ represents hydrogen or the equivalent of an alkali metal ion, analkaline earth metal ion, a copper ion or an iron ion; a quaternary C₁-C₄ -alkylammonium or C₁ -C₄ -hydroxyalkylammonium radical; a C₁ -C₉-alkyl radical that is unsubstituted or mono- or poly-substituted byamino, halogen, hydroxy, cyano, nitro, phenyl C₁ -C₄ -alkoxy, polyethoxyhaving from 2 to 6 ethylene oxide units, --COOR, --COSR, --CONH₂ --,--CON(C₁ -C₄ -alkoxy)-C₁ -C₄ -alkyl, --CO--N-di-C₁ -C₄ -alkyl, --CONH-C₁-C₄ - alkyl, --N(C₁ -C₄ -alkoxy)-C₁ -C₄ -alkyl or by di-C₁ -C₄-alkylamino; a C₃ -C₉ -alkenyl radical that is unsubstituted orsubstituted by halogen or by C₁ -C₄ -alkoxy; or a C₃ -C₉ -alkynylradical that is unsubstituted or substituted by halogen or by C₁ -C₄-alkoxy; C₃ -C₉ -cycloalkyl; or phenyl that is unsubstituted orsubstituted by cyano, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, acetyl, --COOR₁₇,--COSR₁₇, --CONH₂, --CON(C₁ -C₄ -alkoxy)-C₁ -C₄ -alkyl, --CO--N-di-C₁-C₄ -alkyl or by --COHN--C₁ -C₄ -alkyl,

each of R₁₅ and R₁₆, independently of the other, represents C₁ -C₄-alkyl or they together represent a 3- to 6-membered alkylene chain and

R₁₇ represents hydrogen, C₁ -C₆ -alkyl, C₁ -C₆ -haloalkyl, C₂ -C₆-alkoxyalkyl, C₃ -C₆ -alkenyl, C₃ -C₆ -haloalkenyl, C₃ -C₆ -alkynyl orC₃ -C₆ -haloalkynyl.

In the compounds of the formula II, halogen, as an independentsubstituent or as part of another substituent, such as haloalkyl,haloalkoxy, haloalkenyl or haloalkynyl, is fluorine, chlorine, bromineor iodine, among which fluorine and chlorine are preferred.

Depending on the number of carbon atoms present, alkyl is methyl, ethyl,n-propyl, i-propyl or isomeric butyl, pentyl, hexyl, heptyl or octyl.The alkyl groups contained in the radicals alkoxy, alkoxyalkyl,haloalkyl and haloalkoxy are identical. Alkyl groups having a low numberof carbon atoms are preferred in each case.

Preferred haloalkyl radicals, or haloalkyl moieties in haloalkoxyradicals, are: fluoromethyl, difluoromethyl, trifluoromethyl,chloromethyl, trichloromethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl,1,1,2,2-tetrafluoroethyl, perfluoroethyl, 2-chloroethyl,2,2,2-trichloroethyl, 2-bromoethyl and 1,1,2,3,3,3-hexafluoropropyl.

Cycloalkyl is a mono- or bi-cyclic saturated hydrocarbon ring system,such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl,cyclooctyl, cyclononyl, bicyclo[4.3.0]nonyl, bicyclo[5.2.0]nonyl orbicyclo[2.2.2]octyl.

Especially noteworthy is the protective action of pyrazole derivativesof the formula I against herbicides of the formula II in which Trepresents the group --O--R₁₄ or --O--N═CR₁₅ R₁₆ in which R₁₄ representshydrogen, C₁ -C₄ -alkyl or C₃ -C₄ -alkynyl, or C₁ -C₄ -alkyl that issubstituted by C₁ -C₄ -alkoxycarbonyl or by di-C₁ -C₄ -alkylamino, and

each of R₁₅ and R₁₆, independently of the other, represents C₁ -C₄-alkyl or R₁₅ and R₁₆ together represent a C₄ -C₇ -alkylene chain.

Individual meanings of T that should be given special mention aremethoxy, ethoxy, propoxy, isopropoxy, butoxy, dimethylaminoethoxy,propargyloxy, 1-cyano-1-methylethoxy, methoxycarbonylmethylthio,1-ethoxy-carbonylethoxy, butoxycarbonyl, --O--N═C(CH₃)₂, --O--N═C(CH₃)C₂H₅ or --O--N═C(CH₂)₅, and of G: ##STR8## especially2-[4-(6-chlorobenzoxazol-2-yloxy)-phenyoxy]-propionic acid ethyl ester,

2-[4-(6-chloroquinoxalin-3-yloxy)-phenyoxy]-propionic acid ethyl ester,and the

2-[4-(5-chloro-3-fluoropyridin-2-yloxy)-phenyoxy]-propionic acidderivatives in Table 1.

                  TABLE 1                                                         ______________________________________                                         ##STR9##                     (II)                                            No.    Y                   physical constant                                  ______________________________________                                        2.1    OCH.sub.3           m.p. 63-64° C.                              2.2    OC.sub.4 H.sub.9 -n n.sub.D.sup.35 = 1.5275                            2.3    ONC(CH.sub.3).sub.2 n.sub.D.sup.35 = 1.5488                            2.4    OC.sub.2 H.sub.5    n.sub.D.sup.35 = 1.5358                            2.5    OCH.sub.2CH.sub.2N(CH.sub.3).sub.2                                                                n.sub.D.sup.35 = 1.5334                            2.6    OCH.sub.2C CH       n.sub.D.sup.35 = 1.5492                            2.7                                                                                   ##STR10##          n.sub.D.sup.35 = 1.5330                            2.8    SCH.sub.2COOCH.sub.3                                                                              n.sub.D.sup.35 = 1.5607                            2.9                                                                                   ##STR11##          n.sub.D.sup.35 = 1.5227                            2.10   OCH.sub.2COOC.sub.4 H.sub.9 -n                                                                    n.sub.D.sup.35 = 1.5223                            2.11   OC.sub.3 H.sub.7 -n n.sub.D.sup.35 = 1.5319                            2.12   OC.sub.3 H.sub.7 -i n.sub.D.sup.35 = 1.5284                            2.13                                                                                  ##STR12##          n.sub.D.sup.35 = 1.5340                            2.14                                                                                  ##STR13##          n.sub.D.sup.35 = 1.5360                            2.15   OCH.sub.3 (2R)      n.sub.D.sup.35 = 1.5359                            2.16   OH                  m.p. 95-97° C.                              2.17   SCH.sub.2COOCH.sub.3 (2R)                                                                         n.sub.D.sup.35 = 1.5623                            2.18                                                                                  ##STR14##          n.sub.D.sup.35 = 1.5223                            2.19   OCH.sub.2C CH (2R)  m.p. 55-56° C.                              2.20   NHOCH.sub.3         m.p. 103-105° C.                            ______________________________________                                    

Very special mention should be made of compound 2.19 ##STR15## and its2R enantiomer.

The optically active carbon atom of the propionic acid group can bepresent in the R- as well as in the S- configuration. Unless otherwiseindicated, it should be understood that the racemic mixtures areincluded in each case. Preferred herbicides of the formula II have the2R configuration.

As cultivated plants that can be protected by1,5-diphenylpyrazole-3-carboxylic acid derivatives of the formula Iagainst the harmful effects of herbicides of the formula II there comeinto consideration especially those which are important in the food ortextile sector, for example sugar cane and especially sorghum, corn,rice and other types of cereal (wheat, rye, barley, oats).

The invention relates also to the novel1,5-di-phenylpyrazole-3-carboxylic acid derivatives of the formula I##STR16## in which each of R_(a) and R_(b), independently of the other,represents halogen, C₁ -C₅ -alkyl, C₁ -C₅ -haloalkyl, C₂ -C₅ -alkenyl,C₂ -C₅ -alkynyl or cyano, n represents zero or an integer from 1 to 3and R₁ has the meaning given above, with the proviso that, when (R_(a))represents hydrogen, n=1 and R₁ represents hydrogen or ethyl, R_(b),when it represents methyl or halogen, must be in the ortho position.

Important among these derivatives are those in which R_(a), R_(b) and nhave the meanings given under formula I while R₁ represents C₁ -C₁₈-alkyl or C₃ -C₁₈ -cycloalkyl each of which is unsubstituted or mono- orpoly-substituted by C₂ -C₈ -alkenyl, C₂ -C₈ -alkynyl, C₃ -C₈-cycloalkenyl, halogen, cyano, C₁ -C₄ -alkoxy, C₁ -C₄ -alkoxycarbonyl,C₁ -C₄ -alkylcarbonyl, carbamoyl, di(C₁ -C₄ -alkylcarbamoyl), amino, C₁-C₄ -alkylamino or by di(C₁ -C₄ -alkylamino), or R₁ represents a 5- or6-membered heterocycle Q that is bonded via N or C, or a phenyl ornaphthyl radical U or an imido radical --N═C(R₂)R₂, R₂, Q and U havingthe meanings given under formula I, with the proviso that, when (R_(a))nis hydrogen, n=1 and R₁ is hydrogen, (R_(b))n, when it represents methylor halogen, must be in the ortho position.

A very good action is exhibited by the 1,5-diphenylpyrazole-3-carboxylicacid esters of the formula I in which R_(a), R_(b) and n have themeanings given under formula I while R₁ represents C₁ -C₁₈ -alkyl thatis unsubstituted or mono- or poly-substituted by C₂ -C₈ -alkyl, C₂ -C₈-alkynyl, halogen, nitro, cyano, C₁ -C₄ -alkoxy or by phenyl, especiallythe 1,5-diphenylpyrazole-3-carboxylic acid salts of the formula I inwhich R_(a), R_(b) and n have the meanings given under formula I and R₁represents a plant-physiologically tolerable metal or ammonium cation,especially 1-(2-chlorophenyl)-3-methoxycarbonyl-5-phenylpyrazole,1-(2,4-dichlorophenyl)-3-methoxycarbonyl-5-phenylpyrazole and1-(2-chlorophenyl-3-methoxycarbonyl-5-(2-fluorophenyl)pyrazole.

The acid halides of the 1,5-diphenylpyrazole-3-carboxylic acids of theformula I are novel and the invention relates also to these.

The 1,5-diphenylpyrazole-3-carboxylic acid derivatives of the formula Ican be prepared in accordance with various methods of synthesis knownper se. According to a method described in Ber. 25 3143 (1892),3-ethoxycarbonyl-1,5-diphenylpyrazole is prepared by condensing molaramounts of bromoacetophenone and ethyl acetoacetate in the presence ofsodium ethoxide to form 2-acetyl-3-benzoylpropionic acid ethyl ester towhich a molar amount of phenyldiazonium chloride is added. Thecondensate (3-benzoyl-2-phenylhydrazinoximepropionic acid ethyl ester)cyclises at elevated temperature to form3-ethylcarbonyl-1,5-diphenylpyrazole. The reaction sequence can berepresented schematically in the following manner: ##STR17##

According to another process described in Ber. 47, 1435 (1914) and Can.J. Chem. 41, 1813 (1963), it is possible to prepare1,5-diphenylpyrazole-3-carboxylic acid and its ethyl ester by mixingtogether molar amounts of 3-benzoylpropionic acid and acetic anhydrideand adding a molar amount of a phenyldiazonium chloride to the resultingcondensation product 5-phenylfuran-2-carbonyl. The resulting2-phenylhydrazine-5-phenylfurfurylidene condensate cyclises at elevatedtemperature to form the 3-carboxylic acid 1,5-diphenylpyrazole or anester thereof in accordance with the scheme ##STR18## In these formulae,(R_(a)), (R_(b)), and n have the meanings given under formula I andR_(b) represents preferably ortho chlorine or para methyl.

According to a further process analogous to Ber. 20 2185 (1887), it ispossible to prepare 1,5-diphenylpyrazole-3-carboxylic acids and theiresters by condensing equimolar amounts of acetophenone and oxalic aciddimethyl ester in the presence of a base, for example sodium methoxideor ethoxide, to form benzoylpyruvic acid methyl ester, adding anequimolar amount of a phenylhydrazine thereto and cyclising thecondensate in an acidic medium, in accordance with the reaction scheme##STR19## In these formulae R_(a), R_(b) and n have the meanings givenunder formula I.

The process according to the invention for the preparation of the1,5-diphenylpyrazole 3-carboxylic acid esters is characterised in thatan acetophenone of the formula III ##STR20## in which R_(a) and n havethe meanings given under formula I is reacted in an inert organicsolvent in the presence of a base with an equimolar amount of an oxalicacid diester of the formula IV ##STR21## in which R₁ has the meaninggiven under formula I, there is added to the resulting benzoylpyruvicacid ester of the formula V ##STR22## in which R_(a), R₁ and n have themeanings given under formula I an equimolar amount of phenylhydrazine ofthe formula VI ##STR23## in which R_(b) and n have the meanings givenunder formula I, and then the mixture is cyclised in an acidic medium atelevated temperature to form the 1,5-diphenylpyrazole-3-carboxylic acidderivative of the formula I.

Suitable inert solvents for the condensation of the acetophenone and theoxalic acid ester are the corresponding alcohols, such as methanol,ethanol or acetone, higher-boiling ketones, such as methyl ethyl ketoneor dioxan, but also higher-boiling ethers, such as dipropyl ether,tetrahydrofuran, and also aromatic hydrocarbons, such as benzene,toluene and xylene.

The cyclisation of the condensate of benzoylpyruvic acid ester with thehydrazine is carried out in an acidic medium, preferably in glacialacetic acid.

The reaction temperatures are from 0° C. to 200° C. but the operation ispreferably carried out at from 0° C. up to the boiling point of thereaction mixture.

The following methods of synthesis are suitable for the preparation ofthe esters of the 1,5-diphenylpyrazole-3-carboxylic acids of the formulaI: ##STR24## Suitable as acid derivative W are the radicals listed under1.1 to 1.5.

1.1. Halogen or the imidazole radical 1.2. Hydroxy

These reactions run smoothly, in some cases even at room temperature, ina solvent or diluent that is inert towards the reactants. If the acidhalide is used, an equimolar amount of a base is added as acid-bindingagent.

When W is hydroxy, an agent for removing the elements of water, such ascyclohexyldiimide or sulphuric acid, or boiling in a water separator, isalso suitable.

1.3. C₁ -C₄ -alkoxy

The reaction is carried out as an acid-catalysed or base-catalysed esterrearrangement and takes place at elevated temperature (from room toboiling temperature) in an excess of R₁ OH, which may also serve assolvent, and in the presence of a catalytic amount of an acid or base.It is also possible to use as solvent a hydrocarbon, such as benzene,toluene or xylene, cyclohexane, an ether, such as diethyl ether,tetrahydrofuran or dioxan.

1.4. O--CO--C₁ -C₄ -alkyl

The reaction of the acid anhydrides, like that of the halides, takesplace in some cases even at room temperature, in an inert solvent ordiluent If necessary, an equimolar amount of a base is added asacid-binding agent. ##STR25##

In this reaction the amidine radical splits off with the addition of ahydrogen atom as urea. This esterification takes place in an inertanhydrous solvent, advantageously in a hydrocarbon, such as benzene,toluene, xylene or cyclohexane. ##STR26## Halogen or a radical --OSO₂(C₁ -C₄ -alkyl) is suitable as X. The reaction takes place in an organicsolvent or diluent, in the presence of a base, such as, for example, analkali metal alcoholate or an alkali metal or alkaline earth metalcarbonate or hydrogen carbonate. These bases should not be reactivetowards R--X.

The preparation of a 1,5-diphenylpyrazole-3-carboxylic acid esteraccording to the invention is described in the following Example. Thetemperatures are given in degrees Celsius.

Examples of other 1,5-diphenylpyrazole-3-carboxylic acid derivatives ofthe formula I are given in Table 2.

EXAMPLE 1 Manufacture of1-(2-chlorophenyl)-3-methoxycarbonyl-5-phenylpyrazole ##STR27##

(a) 19.3 g (0.105 mol) of 2-chlorophenylhydrazine hydrochloride (97%strength) and 8.6 g (0.105 mol) of sodium acetate are added to asolution of 21.2 g (0.103 mol) of benzoylpyruvic acid methyl ester in100 ml of glacial acetic acid. After the reaction mixture has beenboiled under reflux for 2 hours, it is cooled to room temperature andthen poured into ice-water. The resin formed is taken up in ethylacetate and washed neutral with water and IM soda solution. The organicphase is separated off, dried over sodium sulphate and concentrated in arotary evaporator. The oil that remains is crystallised from diisopropylether. 17.6 g of title product having a melting point of 67°-71° arethus obtained.

The benzoylpyruvic acid methyl ester required as starting material isprepared in the following manner: ##STR28##

b) A mixture of 75 ml (0.405 mol) of 30% sodium methoxide solution and30 ml of methanol is cooled to 0°, and then 48 g (0.4 mol) ofacetophenone are added slowly while stirring. A solution of 47.2 g (0.4mol) of oxalic acid dimethyl ester in 100 ml of methanol is addeddropwise to the mixture while stirring at 8°-10°. The reaction mixturebecomes turbid and finally a thick yellow precipitate is formed whichcan hardly be stirred. Sufficient methanol is added to make it possibleto stir the reaction mixture again. After stirring for a further 3 hoursat room temperature, the whole is filtered with suction and theprecipitate is washed with diethyl ether and subjected to suction untildry. The filter material is suspended in water and adjusted to pH 4 withglacial acetic acid while stirring and cooling whereupon thebenzoylpyruvic acid methyl ester is formed. It is filtered off, washedwith ice-water and dried over phosphorus pentoxide in an desiccator. 42g of ester having a melting point of 56°-58° are obtained.

EXAMPLE 2 Manufacture of1-(2-chlorophenyl)-5-phenylpyrazole-3-carboxylic acid chloride ##STR29##A mixture of 149.4 g of 1-(2-chlorophenyl)-5-phenylpyrazole-3-carboxylicacid and 2000 ml of dry ethylene chloride is heated to 70°. 40 ml ofthionyl chloride are added dropwise thereto over a period of 12 minuteswhile stirring. The reaction mixture is then maintained at refluxtemperature for 21/4 hours, cooled to room temperature and concentratedby evaporation in vacuo. The residue is recrystallised fromcyclohexane/hexane 126 g of the above acid chloride, which has a meltingpoint of 101°-102°, are thus obtained.

                                      TABLE 2                                     __________________________________________________________________________     ##STR30##                             (I)                                    No. (R.sub.a).sub..sbsb.n                                                               (R.sub.b).sub..sbsb.n                                                                 R.sub.1          phys. data                                 __________________________________________________________________________    1   --    2-Cl    CH.sub.3         m.p. 67-70°                         2   --    2-Cl    C.sub.2 H.sub.5                                             3   --    2-Cl    C.sub.3 H.sub.7 -n                                          4   --    2-Cl    CH(CH.sub.3).sub.2                                          5   --    2-Cl    CH.sub.2 CH(CH.sub.3).sub.2                                 6   --    2-Cl    Tetrahydrofurfuryl                                          7   --    2-Cl    CH.sub.2 CH.sub.2 CH(CH.sub.3).sub.2                        8   --    2-Cl    CH.sub.2 CH(C.sub.2 H.sub.5).sub.2                          9   --    2-Cl    CH(CH.sub.3)CH.sub.2 OCH.sub.3                              10  --    2-Cl    CH.sub.2 CH.sub.2 OCH(CH.sub.3).sub.2                       11  --    2-Cl    CH.sub.2 CHCH.sub.2                                         12  --    2-Cl    CH.sub.2 C(CH.sub.3)CH.sub.2                                                                   m.p. 66-70°                         13  --    2-Cl    CH.sub.2 CH.sub.2 Cl                                        14  --    2-Cl    CH.sub.2 CH(CH.sub.3)CH.sub.2 CH.sub.3                      15  --    2-Cl    CH.sub.2 CCH     m.p. 114-115°                       16  --    2-Cl    CH.sub.2 CH.sub.2 CCH                                       17  --    2-Cl    C(CH.sub.3).sub.2 CH.sub.2 CH.sub.3                         18  --    2-Cl    CH(CH.sub.3)COOCH.sub.3                                     19  --    2-Cl    C(CH.sub.3).sub.2 COOC.sub.2 H.sub.5                        20  --    2-Cl    CH.sub.2 CH.sub.2 CN                                        21  --    2-Cl    Pyran-2-ylmethyl                                            22  --    2-Cl    Benzyl           m.p. 142-144°                       23  --    2-Cl    CH.sub.2 CCl.sub.3                                          24  --    2-Cl    Phenoxyethyl     m.p. 84-91°                         25  --    2-Cl    Cyclopropylmethyl                                           26  --    2-Cl    Cyclopentylmethyl                                           27  --    2-Cl    2,2-Dimethyl-1,3-                                                             dioxolan-4-ylmethyl                                         28  --    2-Cl    2-Thenyl         m.p. 147-149°                       29  --    2-Cl    CH.sub.2 CHCHCl                                             30  --    2-Cl    CH.sub.2 C(Cl)CH.sub.2                                      31  --    2-Cl    CH.sub.2 CH.sub.2 Si(CH.sub.3).sub.3                                                           m.p. 88-89°                         32  --    2-Cl    CH.sub.2 Si(CH.sub.3).sub.3                                 33  --    2-Cl    Pyrazol-1-yl-ethyl                                          34  --    2-Cl    CH.sub.2 CH(NO.sub.2)CH.sub.3                               35  --    2-Cl    CH.sub.2 CHCHCH.sub.3                                       36  --    2-Cl    Cyclohexyl       m.p. 144-145°                       37  --    2-Cl    (CH.sub.2).sub.9 CH.sub.3                                   38  --    2-Cl    CH.sub.2 CH.sub.2 N(C.sub.2 H.sub.5).sub.2                  39  --    2-Cl    CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5       40  --    2-Cl    CH.sub.2 CH(Br)CH.sub.2 Br                                  41  --    2-Cl    CH(CH.sub.2 Cl).sub.2                                       42  --    2-Cl    CH.sub.2 CH.sub.2 NO.sub.2                                  43  --    2-Cl    CH.sub.2 C(CH.sub.3).sub.2 N(CH.sub.3).sub.2                44  --    2-Cl    CH(CH.sub.3)CH.sub.2 N(CH.sub.3).sub.2                      45  --    2-Cl    2,6-Dimethylcyclo-                                                            hexyl                                                       46  --    2-Cl    2-Furfuryl                                                  47  --    2-Cl    Morpholinoethyl                                             48  --    2-Cl    CH.sub.2 CN                                                 49  --    2-Cl    Cyclohexylmethyl m.p. 103-104°                       50  --    2-Cl    Pyrazol-1-yl-prop-                                                                             m.p. 91-92°                                           2-yl                                                        51  --    2-Cl    CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.3                         52  --    2-Cl    CH.sub.2 COOCH.sub.3                                                                           m.p. 143-145°                       53  --    2-Cl    CH(CH.sub.3)(CH.sub.2).sub.4 CH.sub.3                                                          n.sub.D.sup.25 1.5470                      54  --    2-Cl    CH(CHCH.sub.2)(CH.sub.2).sub.4 CH.sub.3                     55  --    2,4 Cl.sub.2                                                                          CH.sub.3         m.p. 140-143°                       56  --    2,4 Cl.sub.2                                                                          C.sub.2 H.sub.5                                             57  --    2,4 Cl.sub.2                                                                          CH(CH.sub.3).sub.2                                          58  --    2,4 Cl.sub.2                                                                          CH(CH.sub.3)(CH.sub.2).sub.4 CH.sub.3                       59  --    2,4 Cl.sub.2                                                                          CH.sub.2 CHCH.sub.2                                         60  --    2,4 Cl.sub.2                                                                          CH.sub.2 CCH                                                61  --    2,4 Cl.sub.2                                                                          Benzyl                                                      62  --    2,4 Cl.sub.2                                                                          (CH.sub.2).sub.7 CH.sub.3                                   63  --    2,3 Cl.sub.2                                                                          CH.sub.3                                                    64  --    2,3 Cl.sub.2                                                                          C.sub.2 H.sub.5                                             65  --    2,3 Cl.sub.2                                                                          CH(CH.sub.3).sub.2                                          66  --    2,3 Cl.sub.2                                                                          CH(CH.sub.3)(CH.sub.2).sub.4 CH.sub.3                       67  --    2,3 Cl.sub.2                                                                          CH.sub.2 CHCH.sub.2                                         68  --    2,3 Cl.sub.2                                                                          CH.sub.2 CCH                                                69  --    2,3 Cl.sub.2                                                                          Benzyl                                                                        (CH.sub.2).sub.7 CH.sub.3                                   70  --    2-F     CH.sub.3         m.p. 83-85°                         71  --    2-F     C.sub.2 H.sub.5                                             72  --    2-F     CH(CH.sub.3).sub.2                                          73  --    2-F     CH(CH.sub.3)(CH.sub.2).sub.4 CH.sub.3                       74  --    2-F     CH.sub.2 CHCH.sub.2                                         75  --    2-F     CH.sub.2 CHCH                                               76  --    2-F     Benzyl                                                      77  --    2-F     (CH.sub.2).sub.7 CH.sub.3                                   78  --    2-OCH.sub.3                                                                           CH.sub.3         m.p. 126-128°                       79  --    2-OCH.sub.3                                                                           C.sub.2 H.sub.5                                             80  --    2-OCH.sub.3                                                                           CH(CH.sub.3).sub.2                                          81  --    2-OCH.sub.3                                                                           CH(CH.sub.3)(CH.sub.2).sub.4 CH.sub.3                       82  --    2-OCH.sub.3                                                                           CH.sub.2 CHCH.sub.2                                         83  --    2-OCH.sub.3                                                                           CH.sub.2 CCH                                                84  --    2-OCH.sub.3                                                                           Benzyl                                                      85  --    2-OCH.sub.3                                                                           (CH.sub.2).sub.7 CH.sub. 3                                  86  --    2,5 Cl.sub.2                                                                          CH.sub.3                                                    87  --    2,5 Cl.sub.2                                                                          C.sub.2 H.sub.5                                             88  --    2,5 Cl.sub.2                                                                          CH(CH.sub.3).sub.2                                          89  --    2,5 Cl.sub.2                                                                          CH(CH.sub.3)(CH.sub.2).sub.4 CH.sub.3                       90  --    2,5 Cl.sub.2                                                                          CH.sub.2 CHCH.sub.2                                         91  --    2,5 Cl.sub.2                                                                          CH.sub.2 CCH                                                92  --    2,5 Cl.sub.2                                                                          Benzyl                                                      93  --    2,5 Cl.sub.2                                                                          (CH.sub.2).sub.7 CH.sub.3                                   94  --    2-Cl, 4-CH.sub.3                                                                      CH.sub.3                                                    95  --    2-Cl, 4-CH.sub.3                                                                      C.sub.2 H.sub.5                                             96  --    2-Cl, 4-CH.sub.3                                                                      CH(CH.sub.3).sub.2                                          97  --    2-Cl, 4-CH.sub.3                                                                      CH(CH.sub.3)(CH.sub.2).sub.4 CH.sub.3                       98  --    2-Cl, 4-CH.sub.3                                                                      CH.sub.2 CHCH.sub.2                                         99  --    2-Cl, 4-CH.sub.3                                                                      CH.sub.2 CCH                                                100 --    2-Cl, 4-CH.sub.3                                                                      Benzyl                                                      101 --    2-Cl, 4-CH.sub.3                                                                      (CH.sub.2).sub.7 CH.sub.3                                   102 --    2-Br    CH.sub.3         m.p. 81-83°                         103 --    2-Br    C.sub.2 H.sub. 5                                            104 --    2-Br    CH(CH.sub.3).sub.2                                          105 --    2-Br    CH(CH.sub.3)(CH.sub.2).sub.4 CH.sub.3                       106 --    2-Br    CH.sub.2 CHCH.sub.2                                         107 --    2-Br    CH.sub.2 CCH                                                108 --    2-Br    Benzyl                                                      109 --    2-Br    (CH.sub.2).sub.7 CH.sub.3                                   110 --    2-CH.sub.3                                                                            CH.sub.3         m.p. 105-106°                       111 --    2-CH.sub.3                                                                            C.sub.2 H.sub.5                                             112 --    2-CH.sub.3                                                                            CH(CH.sub.3).sub.2                                          113 --    2-CH.sub.3                                                                            CH(CH.sub.3 )(CH.sub.2).sub.7 CH.sub.3                      114 --    2-CH.sub.3                                                                            CH.sub.2 CHCH.sub.2                                         115       2-CH.sub.3                                                                            CH.sub.2 CCH                                                116 --    2-CH.sub.3                                                                            Benzyl                                                      117 --    2-CH.sub.3                                                                            (CH.sub.2).sub.7 CH.sub.3                                   118 --    2,4 Cl.sub.2, 5-OCH.sub.3                                                             CH.sub.3                                                    119 --    2,4 Cl.sub.2, 5-OCH.sub.3                                                             C.sub.2 H.sub.5                                             120 --    2,4 Cl.sub.2, 5-OCH.sub.3                                                             CH(CH.sub.3).sub.2                                          121 --    2,4 Cl.sub.2, 5-OCH.sub.3                                                             CH(CH.sub.3)(CH.sub.2).sub. 4 CH.sub.3                      122 --    2,4 Cl.sub.2, 5-OCH.sub.3                                                             CH.sub.2 CHCH.sub.2                                         123 --    2,4 Cl.sub.2, 5-OCH.sub.3                                                             CH.sub.2 CCH                                                124 --    2,4 Cl.sub.2, 5-OCH.sub.3                                                             Benzyl                                                      125 --    2,4 Cl.sub.2, 5-OCH.sub.3                                                             (CH.sub.2).sub.7 CH.sub.3                                   126 3-CH.sub.3                                                                          2-Cl    CH.sub.3         m.p. 129-130°                       127 3-Cl  2-Cl    CH.sub.3         m.p. 141-143°                       128 3-OCH.sub.3                                                                         2-Cl    CH.sub.3         m.p. 115-117°                       129 3-F   2-Cl    CH.sub.3         m.p. 114-116°                       130 --    --      CH.sub.3         m.p. 84-85°                         131 --    2-NO.sub.2                                                                            CH.sub.3         m.p. 208-210°                       132 --    --      C.sub.2 H.sub.5  m.p. 85-87°                         133 --    2-Cl                                                                                   ##STR31##                                                  134 --    2-Cl    CH.sub.2 (CH.sub.2).sub.3 CHCH.sub.2                                                           n.sub.D.sup.20 1.5818                      135 --    2-Cl    2-Chlorobenzyl   m.p. 96-98°                         136 --    2-Cl    (CH.sub.2).sub.7 CH.sub.3                                                                      n.sub. D.sup.20 1.5532                     137 --    2-Cl    (CH.sub.2).sub.11CH.sub.3                                                                      m.p. 66-67°                         138 --    2-Cl    5-Chloro-2-methoxy-phenyl-                                                                     m.p. 129-130°                                         ethyl                                                       140 --    2-Cl    Pyridin-3-yl     m.p. 110-111°                       141 --    2-Cl    Pyridin-2-yl                                                142 --    2-Cl    Tetrahydrofuryl-3                                                                              m.p. 95-97°                         143 --    2-Cl    5-Methyl-thiazol-4-ylethyl                                                                     m.p. 90-91°                         144 --    2-Cl    Thiophen-2-yl-ethyl                                                                            m.p. 123-124°                       145 --    2-Cl    (CH.sub.2).sub.3 CH.sub.3                                                                      m.p. 66-68°                         146 --    2-Cl    CH.sub.2CONH.sub.2                                                                             m.p. 192-194°                       147 --    2-Cl    (CH.sub.2).sub.8 CHCH(CH.sub.2).sub.7 CH.sub.3              148 --    2-Cl    HN.sup.⊕ (C.sub.2 H.sub.5).sub.3                                                           m.p. 163-166°                       149 --    2-Cl    H.sub.3 N.sup.⊕ CH(CH.sub.3).sub.2                                                         m.p. 165-168°                       150 --    2-Cl    2,3.4,6.7.8.9.-10-                                                                             m.p. 204-206°                                         Octahydropyrimido-[2,1-a]-                                                    azepin-1-ium                                                151 --    2-Cl    Na.sup.⊕     m.p. >260°                          152 --    2-Cl    H                m.p. 198-200°                       153 --    2-Cl    OR.sub.1 = Cl (acid chloride)                                                                  m.p. 101-102°                       154 --    2-F     OR.sub.1 = Cl (acid chloride)                               155 3-F   2-Fl    OR.sub.1 = Cl (acid chloride)                               156 2-F   --      OR.sub.1 = Cl (acid chloride)                               157 2-Cl  --      OR.sub.1 = Cl (acid chloride)                               158 --    2-CH.sub.3                                                                            OR.sub.1 = Cl (acid chloride)                               159 2-Cl  2,4 (Cl.sub.2)                                                                        CH.sub.3         m.p. 84-88°                         160 2-Cl  2-F     CH.sub.3         m.p. 84-87°                         161 2-F   3-OCH.sub.3                                                                           CH.sub.3         m.p. 114-115°                       162 --    3-OCH.sub.3                                                                           CH.sub.3         m.p. 103-106°                       163 2F, 4Cl                                                                             3-OCH.sub.3                                                                           CH.sub.3         m.p. 82-84°                             SOC.sub.3 H.sub.7 iso                                                     164 2,4-Cl.sub.2                                                                        3-OCH.sub.3                                                                           CH.sub.3         m.p. 109-111°                       165 --    2-Cl    (CH.sub.2).sub.17CH.sub.3                                                                      m.p. 77-79°                         166 --    2-Cl                                                                                   ##STR32##       n.sub.D.sup.20 1.5580                      167 --    2-Cl    CH(CH.sub.2).sub.7 CHCH(CH.sub.2).sub.7 CH.sub.3                                               n.sub.D.sup.22 1.5375                      __________________________________________________________________________

The 1,5-diphenylpyrazole-3-carboxylic acid derivatives of the formula Iaccording to the invention are used as safeners in admixture with2-[4-(phenoxy, pyridin-2-yloxy, 4-benzoxazolyloxy, 4 benzothiazolyloxyand 4-quinoxalin-2-yloxy)-phenoxy]-propionic acid ester herbicides ofthe formula II for controlling weeds in crops of useful plants.

The weeds to be controlled may be both monocotyledonous anddicotyledenous weeds.

There come into consideration as cultivated plants or parts of thoseplants, for example, those mentioned above. Cultivation areas are thoseareas of land in which cultivated plants are already growing or in whichthe seeds of those cultivated plants have already been sown, and alsothe areas of land intended for growing those cultivated plants.

The amount of antidote to be used in relation to the herbicide dependsto a large extent on the method of application. In the case of fieldtreatment that is carried out either by using a tank mix with acombination of antidote and herbicide or by applying the antidote andthe herbicide separately, the ratio of antidote to herbicide isgenerally from 1:100 to 10:1, preferably from 1:20 to 1:1, andespecially 1:1. In contrast, in the case of seed dressing, far smalleramounts of antidote are required per hectare of land under cultivationin relation to the amount of herbicide.

In the case of field treatment, from 0.01 to 10 kg antidote/ha,preferably from 0.05 to 0.5 kg antidote/ha, are normally applied.

In the case of seed dressing, from 0.01 to 10 g antidote/kg seed,preferably from 0.05 to 2 g antidote/kg seed, are normally applied. Ifthe antidote is applied in liquid form by soaking the seeds shortlybefore they are sown it is advantageous to use antidote solutions thatcontain the active ingredient in a concentration of from 1 to 10,000ppm, preferably from 100 to 1000 ppm.

For application, the compounds of the formula I or combinations ofcompounds of the formula I with the herbicides to be antagonised areadvantageously used together with the adjuvants customarily used in theart of formulation and are therefore processed in known manner to form,for example, emulsifiable concentrates, pastes that can be applied as acoating, directly sprayable or dilutable solutions, dilute emulsions,wettable powders, soluble powders, dusts, granulates, and alsoencapsulations in, for example, polymeric substances. As with the natureof the compositions to be used, the methods of application, such asspraying, atomising, dusting, scattering, coating or pouring, are chosenin accordance with the intended objectives and the prevailingcircumstances.

The formulations, i.e. the compositions or preparations containing theactive ingredient of the formula I or a combination of the activeingredient of the formula I and the herbicide to be antagonised and,where appropriate, a solid or liquid adjuvant, are prepared in knownmanner, for example by intimately mixing and/or grinding the activeingredients with extenders, such as, for example, solvents, solidcarriers, and, where appropriate, surface-active compounds(surfactants).

Suitable solvents are: aromatic hydrocarbons, preferably the fractionsC₈ to C₁₂, such as, for example, xylene mixtures or substitutednaphthalenes, phthalic acid esters, such as dibutyl or dioctylphthalate, aliphatic hydrocarbons, such as cyclohexane or paraffins,alcohols and glycols and their ethers and esters, such as ethanol,ethylene glycol, ethylene glycol monomethyl or monoethyl ether, ketones,such as cyclohexanone, strongly polar solvents, such asN-methyl-2-pyrrolidone, dimethyl sulphoxide or dimethylformamide, andalso optionally epoxidised vegetable oils, such as epoxidised coconutoil or soybean oil, or water.

The solid carriers used, for example for dusts and dispersible powders,are generally natural mineral fillers, such as calcite, talcum, kaolin,montmorillonite or attapulgite. In order to improve the physicalproperties it is also possible to add highly dispersed silicic acid orhighly dispersed absorbent polymers. Suitable granulated adsorptivecarriers are porous types, such as, for example, pumice, broken brick,sepiolite or bentonite, and suitable nonsorbent carriers are, forexample, calcite or sand. In addition, it is possible to use a largenumber of pre-granulated materials of inorganic or organic nature, suchas, especially, dolomite or pulverised plant residues.

Depending on the nature of the active ingredient of the formula I to beformulated and optionally also on the nature of the herbicide to beantagonised, suitable surface-active compounds are nonionic, cationicand/or anionic surfactants having good emulsifying, dispersing andwetting properties. The term "surfactants" should also be understood asmeaning mixtures of surfactants.

Suitable anionic surfactants may be both so-called water-soluble soapsand water-soluble synthetic surface-active compounds.

There may be mentioned as soaps the alkali metal salts, alkaline earthmetal salts and unsubstituted or substituted ammonium salts of higherfatty acids (C₁₀ -C₂₂), such as, for example, the sodium or potassium saoleic or stearic acid, or of natural fatty acid mixtures, which can beobtained, for example, from coconut or tallow oil. Fatty acidmethyltaurine salts should also be mentioned.

So-called synthetic surfactants are, however, more often used,especially fatty sulphonates, fatty sulphates, sulphonated benzimidazolederivatives or alkylarylsulphonates.

The fatty sulphonates or fatty sulphates are generally in the form ofalkali metal salts, alkaline earth metal salts or unsubstituted orsubstituted ammonium salts and have an alkyl radical having from 8 to 22carbon atoms, alkyl also including the alkyl moiety of acyl radicals,for example the sodium or calcium salt of lignosulphonic acid, ofdodecylsulphuric acid ester or of a fatty alcohol sulphate mixtureproduced from natural fatty acids. These also include the salts ofsulphuric acid esters and sulphonic acids of fatty alcohol/ethyleneoxide adducts. The sulphonated benzimidazole derivatives containpreferably 2 sulphonic acid groups and one fatty acid radical havingfrom 8 to 22 carbon atoms. Alkylarylsulphonates are, for example, thesodium, calcium or triethanolamine salts of dodecylbenzenesulphonicacid, of dibutylnaphthalenesulphonic acid or of a naphthalenesulphonicacid/formaldehyde condensation product.

Also suitable are corresponding phosphates, such as, for example, saltsof the phosphoric acid ester of an adduct of p-nonylphenol with from 4to 14 moles of ethylene oxide, or phospholipids.

Suitable nonionic surfactants are especially polyglycol etherderivatives of aliphatic or cycloaliphatic alcohols, of saturated orunsaturated fatty acids and of alkylphenols, that may contain from 3 to30 glycol ether groups and from 8 to 20 carbon atoms in the (aliphatic)hydrocarbon radical and from 6 to 18 carbon atoms in the alkyl radicalof the alkylphenols.

Further suitable nonionic surfactants are the water-soluble adducts ofpolyethylene oxide with polypropylene glycol,ethylenediaminopolypropylene glycol and alkylpolypropylene glycolcontaining from 1 to 10 carbon atoms in the alkyl chain, which adductscontain from 20 to 250 ethylene glycol ether groups and from 10 to 100propylene glycol ether groups. The said compounds normally contain from1 to 5 ethylene glycol units per propylene glycol unit.

There may be mentioned as examples of nonionic surfactantsnonylphenolpolyethoxyethanols, castor oil polyglycol ethers,polypropylene/polyethylene oxide adducts,tributylphenoxypolyethoxyethanol, polyethylene glycol andoctylphenoxypolyethoxyethanol.

Also suitable are fatty acid esters of polyoxyethylenesorbitan, such aspolyoxyethylenesorbitan trioleate.

Cationic surfactants are especially quaternary ammonium salts thatcontain, as N-substituent, at least one alkyl radical having from 8 to22 carbon atoms and, as further substituents, lower unsubstituted orhalogenated alkyl, benzyl or lower hydroxyalkyl radicals. The salts arepreferably in the form of halides, methyl sulphates or ethyl sulphates,for example stearyltrimethylammonium chloride orbenzyldi(2-chloroethyl)ethylammonium bromide.

The surfactants customarily employed in the art of formulation aredescribed, inter alia, in the following publications: "McCutcheon'sDetergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood, N.J.,1981. Stache, H., "Tensid-Taschenbuch", Carl Hanser Verlag,Munich/Vienna, 1981.

The agrochemical preparations generally contain from 0.1 to 99% byweight, especially from 0.1 to 95% by weight, active ingredient of theformula I or active ingredient mixture antidote/herbicide, from 1 to99.9% by weight, especially from 5 to 99.8% by weight, solid or liquidadjuvant and from 0 to 25% by weight, especially from 0.1 to 25% byweight, surfactant.

Whereas commercial products will preferably be formulated asconcentrates, the end user will normally employ dilute formulations.

The compositions may also contain other additives, such as stabilisers,anti-foams, viscosity regulators, binders, tackifiers and alsofertilisers or other active ingredients in order to achieve specialeffects.

There are various suitable methods and techniques for using compounds ofthe formula I or compositions containing them for the protection ofcultivated plants against the harmful effects of herbicides of theformula II; the following are examples:

i) Seed Dressing

a) Dressing the seeds with an active ingredient of formula I, formulatedas a wettable powder, by agitating in a vessel until uniformlydistributed on the seed surface (dry dressing). Approximately from 1 to500 g of active ingredient of formula I (from 4 g to 2 kg of wettablepowder) are used per 100 kg of seeds.

b) Dressing the seeds with an emulsifiable concentrate of the activeingredient of formula I according to method a) (wet dressing).

c) Dressing by immersing the seeds in a liquor containing 50-3200 ppm ofactive ingredient of formula I for from 1 to 72 hours and, if desired,subsequently drying the seeds (immersion dressing).

Dressing the seeds or treating the germinated seedlings are naturallythe preferred methods of application because the treatment with theactive ingredient is directed exclusively at the target crop. Generally,from 1 to 500 g of antidote, preferably from 5 to 250 g of antidote, areused per 100 kg of seeds, but the amount may be higher or lower than thelimit concentrations specified depending on the methodology, which alsoallows the addition of other active ingredients or micronutrients(repeat dressing).

ii) Application from a Tank Mix

A liquid preparation produced from a mixture of antidote and herbicide(quantitative ratio from 10:1 to 1:100) is used, the rate of applicationof herbicide being from 0.1 to 10 kg per hectare. Such a tank mix isapplied before or after sowing.

iii) Application in the Seed Furrow

The antidote is introduced into the open sown seed furrow in the form ofan emulsifiable concentrate, wettable powder or granulate and, after theseed furrow has been covered, the herbicide is applied in the normalmanner in the pre-emergence process.

iv) Controlled Release of Active Ingredient

The active ingredient of formula I is applied in solution onto mineralgranulated carriers or polymerised granulates (urea/formaldehyde) andleft to dry. If desired, a coating may be applied (coated granulates)which makes it possible to release the active ingredient in controlledamounts over a predetermined period of time.

Formulation Examples for Liquid Active Ingredients of the Formula I(%=per cent by weight)

    ______________________________________                                        1. Emulsifiable concentrates                                                                       (a)      (b)    (c)                                      ______________________________________                                        active ingredient from Table 2                                                                     25%      40%    50%                                      calcium dodecylbenzenesulphonate                                                                    5%       8%     6%                                      castor oil-polyethylene glycol ether                                                                5%      --     --                                       (36 mols of ethylene oxide)                                                   tributylphenol-polyethylene glycol                                                                 --       12%     4%                                      ether (30 mols of ethylene oxide)                                             cyclohexanone        --       15%    20%                                      xylene mixture       65%      25%    20%                                      ______________________________________                                    

Emulsions of any desired concentration can be produced from suchconcentrates by dilution with water.

    ______________________________________                                        2. Solutions        (a)    (b)    (c)   (d)                                   ______________________________________                                        active ingredient from Table 2                                                                    80%    10%    5%    95%                                   ethylene glycol monomethyl ether                                                                  20%    --     --    --                                    polyethylene glycol MW 400                                                                        --     70%    --    --                                    N-methyl-2-pyrrolidone                                                                            --     20%    --    --                                    epoxidised coconut oil                                                                            --     --     1%     5%                                   benzine (boiling range 160-190° C.)                                                        --     --     94%   --                                    ______________________________________                                    

The solutions are suitable for use in the form of extremely finedroplets.

    ______________________________________                                        3. Granulates         (a)    (b)                                              ______________________________________                                        active ingredient from Table 2                                                                       5%    10%                                              kaolin                94%    --                                               highly dispersed silicic acid                                                                        1%    --                                               attapulgite           --     90%                                              ______________________________________                                    

The active ingredient is dissolved in methylene chloride, sprayed ontothe carrier and the solvent is then evaporated off in vacuo.

    ______________________________________                                        4. Dusts             (a)     (b)                                              ______________________________________                                        active ingredient from Table 2                                                                     2%      5%                                               highly dispersed silicic acid                                                                      1%      5%                                               talcum               97%     --                                               kaolin               --      90%                                              ______________________________________                                    

Dusts that are ready for use are obtained by ultimately mixing thecarriers with the active ingredient.

Formulation Examples for Solid Active Ingredients of the Formula I(%=per cent by weight)

    ______________________________________                                        5. Wettable powders  (a)      (b)    (c)                                      ______________________________________                                        active ingredient from                                                                             25%      50%    75%                                      Table 2                                                                       sodium lignosulphonate                                                                             5%        5%    --                                       sodium lauryl sulphate                                                                             3%       --      5%                                      sodium diisobutylnaphthalene-                                                                      --        6%    10%                                      sulphonate                                                                    octylphenolpolyethylene glycol                                                                     --        2%    --                                       ether (7-8 mols of ethylene oxide)                                            highly dispersed silicic acid                                                                      5%       10%    10%                                      kaolin               62%      27%    --                                       ______________________________________                                    

The active ingredient is mixed well with the additives and thoroughlygrounded in a suitable mill Wettable powders are obtained which can bediluted with water to form suspensions of any desired concentration.

    ______________________________________                                        6. Emulsifiable concentrate                                                   ______________________________________                                        active ingredient from Table 2                                                                       10%                                                    octylphenolpolyethylene glycol                                                                        3%                                                    ether (4-5 mols of ethylene                                                   oxide)                                                                        calcium dodecylbenzenesulphonate                                                                      3%                                                    castor oil polyglycol ether                                                                           4%                                                    (35 mols of ethylene oxide)                                                   cyclohexanone          30%                                                    xylene mixture         50%                                                    ______________________________________                                    

Emulsions of any desired concentration can be prepared from thisconcentrate by dilution with water.

    ______________________________________                                        7. Dusts              (a)    (b)                                              ______________________________________                                        active ingredient from Table 2                                                                       5%     8%                                              talcum                95%    --                                               kaolin                --     92%                                              ______________________________________                                    

Dusts that are ready for use are obtained by mixing the activeingredient with the carriers and grinding in a suitable mill.

    ______________________________________                                        8. Extruder granulate                                                         ______________________________________                                        active ingredient from Table 2                                                                     10%                                                      sodium lignosulphonate                                                                              2%                                                      carboxymethylcellulose                                                                              1%                                                      kaolin               87%                                                      ______________________________________                                    

The active ingredient is mixed with the additives, ground and moistenedwith water. This mixture is extruded and then dried in an air stream.

    ______________________________________                                        9. Coated granulate                                                           ______________________________________                                        active ingredient from Table 2                                                                      3%                                                      polyethylene glycol (MW 200)                                                                        3%                                                      kaolin               94%                                                      ______________________________________                                    

The finely ground active ingredient is uniformly applied in a mixer tothe kaolin moistened with polyethylene glycol. A dust-free coatedgranulate is obtained in this manner.

    ______________________________________                                        10. Suspension concentrate                                                    ______________________________________                                        active ingredient from Table 2                                                                         40%                                                  ethylene glycol          10%                                                  nonylphenolpolyethylene glycol                                                                         6%                                                   ether (15 mols of ethylene oxide)                                             sodium lignosulphonate   10%                                                  carboxymethylcellulose   1%                                                   37% aqueous formaldehyde 0.2%                                                 solution                                                                      silicone oil in the form of                                                                            0.8%                                                 a 75% aqueous emulsion                                                        water                    32%                                                  ______________________________________                                    

The finely ground active ingredient is intimately mixed with theadditives. In this manner, a suspension concentrate is obtained fromwhich suspensions of any desired concentration can be prepared bydilution with water.

Formulation Examples for Active Ingredient Mixtures (Liquid) (%=per centby weight)

    ______________________________________                                        11. Emulsifiable concentrates                                                                      (a)     (b)    (c)                                       ______________________________________                                        active ingredient mixture: antidote                                                                25%     40%    50%                                       from Table 2 and a herbicide from                                             Table 1 in a ratio of 1:1                                                     calcium dodecylbenzenesulphonate                                                                    5%      8%     6%                                       castor oil-polyethylene glycol ether                                                                5%     --     --                                        (36 mols of ethylene oxide)                                                   tributylphenol-polyethylene glycol                                                                 --      12%     4%                                       ether (30 mols of ethylene oxide)                                             cyclohexanone        --      15%    20%                                       xylene mixture       65%     25%    20%                                       ______________________________________                                    

Emulsions of any desired concentration can be produced from suchconcentrations by dilution with water.

    ______________________________________                                        12. Emulsifiable concentrates                                                                      (a)     (b)    (c)                                       ______________________________________                                        active ingredient mixture: antidote                                                                25%     40%    50%                                       from Table 2 and a herbicide from                                             Table 1 in a ratio of 1:3                                                     calcium dodecylbenzenesulphonate                                                                    5%      8%     6%                                       castor oil-polyethylene glycol ether                                                                5%     --     --                                        (36 mols of ethylene oxide)                                                   tributylphenol-polyethylene glycol                                                                 --      12%     4%                                       ether (30 mols of ethylene oxide)                                             cyclohexanone        --      15%    20%                                       xylene mixture       65%     25%    20%                                       ______________________________________                                    

Emulsions of any desired concentration can be produced from suchconcentrates by dilution with water.

    ______________________________________                                        13. Emulsifiable concentrates                                                                      (a)     (b)    (c)                                       ______________________________________                                        active ingredient mixture: antidote                                                                25%     40%    50%                                       from Table 2 and a herbicide from                                             Table 1 in a ratio of 2:1                                                     calcium dodecylbenzenesulphonate                                                                    5%      8%     6%                                       castor oil-polyethylene glycol ether                                                                5%     --     --                                        (36 mols of ethylene oxide)                                                   tributylphenol-polyethylene glycol                                                                 --      12%     4%                                       ether (30 mols of ethylene oxide)                                             cyclohexanone        --      15%    20%                                       xylene mixture       65%     25%    20%                                       ______________________________________                                    

Emulsions of any desired concentration can be produced from suchconcentrates by dilution with water.

    ______________________________________                                        14. Emulsifiable concentrates                                                                       (a)     (b)    (c)                                      ______________________________________                                        active ingredient mixture: antidote                                                                 25%     40%    50%                                      from Table 2 and 2-[4-(5-chloro-3-fluoro-                                     pyridin-2-yloxy)-phenoxy]-propionic acid                                      methyl ester in a ratio of 1:1                                                calcium dodecylbenzenesulphonate                                                                     5%      8%     6%                                      castor oil-polyethylene glycol ether                                                                 5%     --     --                                       (36 mols of ethylene oxide)                                                   tributylphenol-polyethylene glycol                                                                  --      12%     4%                                      ether (30 mols of ethylene oxide)                                             cyclohexanone         --      15%    20%                                      xylene mixture        65%     25%    20%                                      ______________________________________                                    

Emulsions of any desired concentration can be produced from suchconcentrates by dilution with water.

    ______________________________________                                        15. Emulsifiable concentrates                                                                       (a)     (b)    (c)                                      ______________________________________                                        active ingredient mixture: antidote                                                                 25%     40%    50%                                      from Table 2 and 2-[4-(5-chloro-3-fluoro-                                     pyridin-2-yloxy)-phenoxy]-propionic acid                                      methyl ester in a ratio of 1:3                                                calcium dodecylbenzenesulphonate                                                                     5%      8%     6%                                      castor oil-polyethylene glycol ether                                                                 5%     --     --                                       (36 mols of ethylene oxide)                                                   tributylphenol-polyethylene glycol                                                                  --      12%     4%                                      ether (30 mols of ethylene oxide)                                             cyclohexanone         --      15%    20%                                      xylene mixture        65%     25%    20%                                      ______________________________________                                    

Emulsions of any desired concentration can be produced from suchconcentrates by dilution with water.

    ______________________________________                                        16. Solutions       (a)    (b)     (c)  (d)                                   ______________________________________                                        active ingredient mixture: antidote                                                               80%    10%      5%  95%                                   from Table 2 and a herbicide from                                             Table 1 in a ratio of 1:4                                                     ethylene glycol monomethyl ether                                                                  20%    --      --   --                                    polyethylene glycol MW 400                                                                        --     70%     --   --                                    N-methyl-2-pyrrolidone                                                                            --     20%     --   --                                    epoxidised coconut oil                                                                            --     --       1%   5%                                   benzine (boiling range 160-190° C.)                                                        --     --      94%  --                                    ______________________________________                                    

The solutions are suitable for use in the form of extremely finedroplets.

    ______________________________________                                        17. Solutions       (a)    (b)     (c)  (d)                                   ______________________________________                                        active ingredient mixture: antidote                                                               80%    10%      5%  95%                                   from Table 2 and a herbicide from                                             Table 1 in a ratio of 5:2                                                     ethylene glycol monomethyl ether                                                                  20%    --      --   --                                    polyethylene glycol MW 400                                                                        --     70%     --   --                                    N-methyl-2-pyrrolidone                                                                            --     20%     --   --                                    epoxidised coconut oil                                                                            --     --       1%   5%                                   benzine (boiling range 160-190° C.)                                                        --     --      94%  --                                    ______________________________________                                    

The solutions are suitable for use in the form of extremely finedroplets.

    ______________________________________                                        18. Solutions       (a)    (b)     (c)  (d)                                   ______________________________________                                        active ingredient mixture: antidote                                                               80%    10%      5%  95%                                   from Table 2 and a herbicide from                                             Table 1 in a ratio of 1:1                                                     ethylene glycol monomethyl ether                                                                  20%    --      --   --                                    polyethylene glycol MW 400                                                                        --     70%     --   --                                    N-methyl-2-pyrrolidone                                                                            --     20%     --   --                                    epoxidised coconut oil                                                                            --     --       1%   5%                                   benzine (boiling range 160-190° C.)                                                        --     --      94%  --                                    ______________________________________                                    

The solutions are suitable for use in the form of extremely finedroplets.

    ______________________________________                                        19. Solutions      a)     b)      c)    d)                                    ______________________________________                                        active ingredient mixture: antidote                                                              80%    10%     5%    95%                                   from Table 2 and 2-[4-(5-chloro-3-                                            fluoropyridin-2-yloxy)-phenoxy]-                                              propionic acid methyl ester in                                                a ratio of 1:1                                                                ethylene glycol monomethyl ether                                                                 20%    --      --    --                                    polyethylene glycol MW 400                                                                       --     70%     --    --                                    N-methyl-2-pyrrolidone                                                                           --     20%     --    --                                    epoxidised coconut oil                                                                           --     --      1%     5%                                   benzine (boiling range 160-190° C.)                                                       --     --      94%   --                                    ______________________________________                                    

The solutions are suitable for use in the form of extremely finedroplets.

    ______________________________________                                        20. Solutions      a)     b)      c)    d)                                    ______________________________________                                        active ingredient mixture: antidote                                                              80%    10%     5%    95%                                   from Table 2 and 2-[4-(5-chloro-3-                                            fluoropyridin-2-yloxy)-phenoxy]-                                              propionic acid methyl ester in a                                              ratio of 1:4                                                                  ethylene glycol monomethyl ether                                                                 20%    --      --    --                                    polyethylene glycol MW 400                                                                       --     70%     --    --                                    N-methyl-2-pyrrolidone                                                                           --     20%     --    --                                    epoxidised coconut oil                                                                           --     --      1%     5%                                   benzine (boiling range 160-190° C.)                                                       --     --      94%   --                                    ______________________________________                                    

The solutions are suitable for use in the form of extremely finedroplets.

    ______________________________________                                        21. Granulates        a)      b)                                              ______________________________________                                        active ingredient mixture: antidote                                                                 5%      10%                                             from Table 2 and a herbicide from                                             Table 1 in a ratio of 1:1                                                     kaolin                94%     --                                              highly dispersed silicic acid                                                                       1%      --                                              attapulgite           --      90%                                             ______________________________________                                    

The active ingredient is dissolved in methylene chloride, sprayed ontothe carrier and the solvent is then evaporated off in vacuo.

    ______________________________________                                        22. Granulates           a)      b)                                           ______________________________________                                        active ingredient mixture: antidote                                                                    5%      10%                                          from Table 2 and 2-[4-(5-chloro-3-fluoro-                                     pyridin-2-yloxy)-phenoxy]-propionic acid                                      methyl ester in a ratio of 1:1                                                kaolin                   94%     --                                           highly dispersed silicic acid                                                                          1%      --                                           attapulgite              --      90%                                          ______________________________________                                    

The active ingredient is dissolved in methylene chloride, sprayed ontothe carrier and the solvent is then evaporated off in vacuo.

    ______________________________________                                        23. Dusts             a)      b)                                              ______________________________________                                        active ingredient mixture: antidote                                                                 2%      5%                                              from Table 2 and a herbicide from                                             Table 2 in a ratio of 1:1                                                     highly dispersed silicic acid                                                                       1%      5%                                              talcum                97%     --                                              kaolin                --      90%                                             ______________________________________                                    

Dusts that are ready for use are obtained by ultimately mixing thecarriers with the active ingredient.

Formulation Examples for Active Ingredient Mixtures (Solid) (%=per centby weight)

    ______________________________________                                        24. Wettable powders                                                                              a)       b)      c)                                       ______________________________________                                        active ingredient mixture: antidote                                                               25%      50%     75%                                      from Table 2 and a herbicide from                                             Table 1 in a ratio of 1:1                                                     sodium lignosulphonate                                                                            5%        5%     --                                       sodium lauryl sulphate                                                                            3%       --       5%                                      sodium diisobutylnaphthalene-                                                                     --        6%     10%                                      sulphonate                                                                    octylphenolpolyethylene glycol                                                                    --        2%     --                                       ether (7-8 mols of ethylene oxide)                                            highly dispersed silicic acid                                                                     5%       10%     10%                                      kaolin              62%      27%     --                                       ______________________________________                                    

The active ingredient is mixed well with the additives and thoroughlyground in a suitable mill. Wettable powders are obtained which can bediluted with water to form suspensions of any desired concentration.

    ______________________________________                                        25. Wettable powders                                                                              a)       b)      c)                                       ______________________________________                                        active ingredient mixture: antidote                                                               25%      50%     75%                                      from Table 2 and a herbicide from                                             Table 1 in a ratio of 1:4                                                     sodium lignosulphonate                                                                            5%        5%     --                                       sodium lauryl sulphate                                                                            3%       --       5%                                      sodium diisobutylnaphthalene-                                                                     --        6%     10%                                      sulphonate                                                                    octylphenolpolyethylene glycol                                                                    --        2%     --                                       ether (7-8 mols of ethylene oxide)                                            highly dispersed silicic acid                                                                     5%       10%     10%                                      kaolin              62%      27%     --                                       ______________________________________                                    

The active ingredient is mixed well with the additives and thoroughlyground in a suitable mill. Wettable powders are obtained which can bediluted with water to form suspensions of any desired concentration.

    ______________________________________                                        26. Wettable powders                                                                              a)       b)      c)                                       ______________________________________                                        active ingredient mixture: antidote                                                               25%      50%     75%                                      from Table 2 and a herbicide from                                             Table 1 in a ratio of 3:1                                                     sodium lignosulphonate                                                                            5%        5%     --                                       sodium lauryl sulphate                                                                            3%       --       5%                                      sodium diisobutylnaphthalene-                                                                     --        6%     10%                                      sulphonate                                                                    octylphenolpolyethylene glycol                                                                    --        2%     --                                       ether (7-8 mols of ethylene oxide)                                            highly dispersed silicic acid                                                                     5%       10%     10%                                      kaolin              62%      27%     --                                       ______________________________________                                    

The active ingredient is mixed well with the additives and thoroughlyground in a suitable mill. Wettable powders are obtained which can bediluted with water to form suspensions of any desired concentration.

    ______________________________________                                        27. Emulsifiable concentrate                                                  ______________________________________                                        active ingredient mixture: antidote                                                                  10%                                                    from Table 2 and a herbicide from                                             Table 1 in a ratio of 1:1                                                     octylphenolpolyethylene glycol                                                                        3%                                                    ether (4-5 mols of ethylene                                                   oxide)                                                                        calcium dodecylbenzenesulphonate                                                                      3%                                                    castor oil polyglycol ether                                                                           4%                                                    (35 mols of ethylene oxide)                                                   cyclohexanone          30%                                                    xylene mixture         50%                                                    ______________________________________                                    

Emulsions of any desired concentration can be prepared from thisconcentrate by dilution with water.

    ______________________________________                                        28. Emulsifiable concentrate                                                  ______________________________________                                        active ingredient mixture: antidote                                                                  10%                                                    from Table 2 and a herbicide from                                             Table 1 in a ratio of 5:2                                                     octylphenolpolyethylene glycol                                                                        3%                                                    ether (4-5 mols of ethylene                                                   oxide)                                                                        calcium dodecylbenzenesulphonate                                                                      3%                                                    castor oil polyglycol ether                                                                           4%                                                    (35 mols of ethylene oxide)                                                   cyclohexanone          30%                                                    xylene mixture         50%                                                    ______________________________________                                    

Emulsions of any desired concentration can be prepared from thisconcentrate by dilution with water.

    ______________________________________                                        29. Emulsifiable concentrate                                                  ______________________________________                                        active ingredient mixture: antidote                                                                  10%                                                    from Table 2 and a herbicide from                                             Table 1 in a ratio of 1:4                                                     octylphenolpolyethylene glycol                                                                        3%                                                    ether (4-5 mols of ethylene                                                   oxide)                                                                        calcium dodecylbenzenesulphonate                                                                      3%                                                    castor oil polyglycol ether                                                                           4%                                                    (35 mols of ethylene oxide)                                                   cyclohexanone          30%                                                    xylene mixture         50%                                                    ______________________________________                                    

Emulsions of any desired concentration can be prepared from thisconcentrate by dilution with water.

    ______________________________________                                        30. Dusts              a)     b)                                              ______________________________________                                        active ingredient mixture: antidote                                                                  5%      8%                                             from Table 2 and a herbicide from                                             Table 1 in a ratio of 1:1                                                     talcum                 95%    --                                              kaolin                 --     92%                                             ______________________________________                                    

Dusts that are ready for use are obtained by mixing the activeingredient with the carriers and grinding in a suitable mill.

    ______________________________________                                        31. Extruder granulate                                                        ______________________________________                                        active ingredient mixture: antidote                                                                  10%                                                    from Table 2 and a herbicide from                                             Table 1 in a ratio of 1:1                                                     sodium lignosulphonate  2%                                                    carboxymethylcellulose  1%                                                    kaolin                 87%                                                    ______________________________________                                    

The active ingredient is mixed with the additives, ground and moistenedwith water. This mixture is extruded and then dried in an air stream.

    ______________________________________                                        32. Coated granulate                                                          ______________________________________                                        active ingredient mixture: antidote                                                                 3%                                                      from Table 2 and a herbicide from                                             Table 1 in a ratio of 1:1                                                     polyethylene glycol (MW 200)                                                                        3%                                                      kaolin                94%                                                     ______________________________________                                    

The finely ground active ingredient is uniformly applied in a mixer tothe kaolin moistened with polyethylene glycol. A dust-free coatedgranulate is obtained in this manner.

    ______________________________________                                        33. Suspension concentrate                                                    ______________________________________                                        active ingredient mixture: antidote                                                                 40%                                                     from Table 2 and a herbicide from                                             Table 1 in a ratio of 1:1                                                     ethylene glycol       10%                                                     nonylphenolpolyethylene glycol                                                                       6%                                                     ether (15 mols of ethylene oxide)                                             sodium lignosulphonate                                                                              10%                                                     carboxymethylcellulose                                                                               1%                                                     37% aqueous formaldehyde solution                                                                   0.2%                                                    silicone oil in the form of                                                                         0.8%                                                    a 75% aqueous emulsion                                                        water                 32%                                                     ______________________________________                                    

The finely ground active ingredient is intimately mixed with theadditives. In this manner, a suspension concentrate is obtained fromwhich suspensions of any desired concentration can be prepared bydilution with water.

    ______________________________________                                        34. Suspension concentrate                                                    ______________________________________                                        active ingredient mixture: antidote                                                                   40%                                                   from Table 2 and a herbicide from Table                                       1 in a ratio of 1:4                                                           ethylene glycol         10%                                                   nonylphenolpolyethylene glycol                                                                         6%                                                   ether (15 mols of ethylene oxide)                                             sodium lignosulphonate  10%                                                   carboxymethylcellulose   1%                                                   37% aqueous formaldehyde solution                                                                     0.2%                                                  silicone oil in the form of                                                                           0.8%                                                  a 75% aqueous emulsion                                                        water                   32%                                                   ______________________________________                                         concentrate is obtained from which suspensions of any desired     concentration can be prepared by dilution with water.

    ______________________________________                                        35. Suspension concentrate                                                    ______________________________________                                        active ingredient mixture: antidote                                                                 40%                                                     from Table 2 and a herbicide from                                             Table 1 in a ratio of 3:1                                                     ethylene glycol       10%                                                     nonylphenolpolyethylene glycol                                                                       6%                                                     ether (15 mols of ethylene oxide)                                             sodium lignosulphonate                                                                              10%                                                     carboxymethylcellulose                                                                               1%                                                     37% aqueous formaldehyde solution                                                                   0.2%                                                    silicone oil in the form of                                                                         0.8%                                                    a 75% aqueous emulsion                                                        water                 32%                                                     ______________________________________                                    

The finely ground active ingredient is intimately mixed with theadditives. In this manner, a suspension concentrate is obtained fromwhich suspensions of any desired concentration can be prepared bydilution with water.

BIOLOGICAL EXAMPLE Test Description

In a greenhouse, seeds of the plants to be tested are placed in plasticspots containing 0.5 l of soil. When the plants have reached the 2- to3-leaf stage, a safener of formula I and a herbicide of formula II areapplied together in the form of a tank mix. 21 days after theapplication the condition of the plants is evaluated and the protectiveaction of the safener is assessed. The assessment is based on thedifference between the damage caused by the herbicide to a plant thathas not been treated with the safener and the damage caused by theherbicide to a plant that has been treated with safener. The protectiveaction is given as a percentage.

The results are given in the Table below.

    ______________________________________                                        Results:                                                                      Crop: Spring-sown wheat "Besso"                                               Herbicide:                                                                    2(R)-2-[4-(5-chloro-3-fluoropyridin-2-yloxy)-phenoxy]-                        propionic acid propargyl ester (Table 1, 2.19 2R-enantiomer)                                         (Table 2)                                              rate of application                                                                       antidote   rate of   protective                                   of herbicide                                                                              No.        application                                                                             action                                       ______________________________________                                        400 g/ha    001        400 g/ha  75%                                                                 200 g/ha  75%                                                                 100 g/ha  75%                                                                  50 g/ha  75%                                          200 g/ha    001        400 g/ha  63%                                                                 200 g/ha  75%                                                                 100 g/ha  63%                                                                  50 g/ha  75%                                          100 g/ha    001        400 g/ha  50%                                                                 200 g/ha  63%                                                                 100 g/ha  63%                                                                  50 g/ha  63%                                          400 g/ha    012        400 g/ha  88%                                                                 200 g/ha  75%                                                                 100 g/ha  75%                                                                  50 g/ha  75%                                          200 g/ha    012        400 g/ha  75%                                                                 200 g/ha  75%                                                                 100 g/ha  63%                                                                  50 g/ha  63%                                          100 g/ha    012        400 g/ha  50%                                                                 200 g/ha  63%                                                                 100 g/ha  63%                                                                  50 g/ha  63%                                          400 g/ha    024        400 g/ha  88%                                                                 200 g/ha  88%                                                                 100 g/ha  88%                                                                  50 g/ha  75%                                          200 g/ha    024        400 g/ha  75%                                                                 200 g/ha  75%                                                                 100 g/ha  75%                                                                  50 g/ha  75%                                          100 g/ha    024        400 g/ha  63%                                                                 200 g/ha  63%                                                                 100 g/ha  63%                                                                  50 g/ha  63%                                          400 g/ha    036        400 g/ha  50%                                                                 200 g/ha  50%                                                                 100 g/ha  50%                                                                  50 g/ha  38%                                          200 g/ha    036        400 g/ha  63%                                                                 200 g/ha  75%                                                                 100 g/ha  75%                                                                  50 g/ha  50%                                          100 g/ha    036        400 g/ha  50%                                                                 200 g/ha  50%                                                                 100 g/ha  63%                                                                  50 g/ha  50%                                          400 g/ha    049        400 g/ha  63%                                                                 200 g/ha  63%                                                                 100 g/ha  63%                                                                  50 g/ha  38%                                          200 g/ha    049        400 g/ha  75%                                                                 200 g/ha  88%                                                                 100 g/ha  75%                                                                  50 g/ha  75%                                          100 g/ha    049        400 g/ha  50%                                                                 200 g/ha  63%                                                                 100 g/ha  63%                                                                  50 g/ha  50%                                          400 g/ha    050        400 g/ha  63%                                                                 200 g/ha  63%                                                                 100 g/ha  50%                                                                  50 g/ha  50%                                          200 g/ha    050        400 g/ha  63%                                                                 200 g/ha  75%                                                                 100 g/ha  75%                                                                  50 g/ha  63%                                          100 g/ha    050        400 g/ha  50%                                                                 200 g/ha  50%                                                                 100 g/ha  63%                                                                  50 g/ha  38%                                          400 g/ha    052        400 g/ha  88%                                                                 200 g/ha  75%                                                                 100 g/ha  75%                                                                  50 g/ha  88%                                          200 g/ha    052        400 g/ha  75%                                                                 200 g/ha  75%                                                                 100 g/ha  75%                                                                  50 g/ha  75%                                          100 g/ha    052        400 g/ha  63%                                                                 200 g/ha  63%                                                                 100 g/ha  63%                                                                  50 g/ha  63%                                          400 g/ha    055        400 g/ha  50%                                                                 200 g/ha  50%                                                                 100 g/ha  50%                                                                  50 g/ha  50%                                          200 g/ha    055        400 g/ha  63%                                                                 200 g/ha  63%                                                                 100 g/ha  75%                                                                  50 g/ha  63%                                          100 g/ha    055        400 g/ha  63%                                                                 200 g/ha  63%                                                                 100 g/ha  63%                                                                  50 g/ha  63%                                          400 g/ha    070        400 g/ha  63%                                                                 200 g/ha  63%                                                                 100 g/ha  50%                                                                  50 g/ha  80%                                          200 g/ha    070        400 g/ha  63%                                                                 200 g/ha  75%                                                                 100 g/ha  75%                                                                  50 g/ha  63%                                          100 g/ha    070        400 g/ha  50%                                                                 200 g/ha  63%                                                                 100 g/ha  50%                                                                  50 g/ha  63%                                          400 g/ha    102        400 g/ha  63%                                                                 200 g/ha  75%                                                                 100 g/ha  63%                                                                  50 g/ha  50%                                          200 g/ha    102        400 g/ha  63%                                                                 200 g/ha  63%                                                                 100 g/ha  75%                                                                  50 g/ha  75%                                          100 g/ha    102        400 g/ha  50%                                                                 200 g/ha  50%                                                                 100 g/ha  50%                                                                  50 g/ha  50%                                          400 g/ha    129        400 g/ha  63%                                                                 200 g/ha  63%                                                                 100 g/ha  63%                                                                  50 g/ha  50%                                          200 g/ha    129        400 g/ha  63%                                                                 200 g/ha  63%                                                                 100 g/ha  75%                                                                  50 g/ha  50%                                          100 g/ha    129        400 g/ha  50%                                                                 200 g/ha  50%                                                                 100 g/ha  50%                                                                  50 g/ha  50%                                          400 g/ha    132        400 g/ha  75%                                                                 200 g/ha  63%                                                                 100 g/ha  50%                                                                  50 g/ha  38%                                          200 g/ha    132        400 g/ha  63%                                                                 200 g/ha  75%                                                                 100 g/ha  63%                                                                  50 g/ha  63%                                          100 g/ha    132        400 g/ha  63%                                                                 200 g/ha  63%                                                                 100 g/ha  63%                                                                  50 g/ha  63%                                          400 g/ha    134        400 g/ha  75%                                                                 200 g/ha  63%                                                                 100 g/ha  63%                                                                  50 g/ha  38%                                          200 g/ha    134        400 g/ha  75%                                                                 200 g/ha  75%                                                                 100 g/ha  75%                                                                  50 g/ha  63%                                          100 g/ha    134        400 g/ha  50%                                                                 200 g/ha  63%                                                                 100 g/ha  50%                                                                  50 g/ha  50%                                          400 g/ha    135        400 g/ha  88%                                                                 200 g/ha  88%                                                                 100 g/ha  88%                                                                  50 g/ha  88%                                          200 g/ha    135        400 g/ha  75%                                                                 200 g/ha  75%                                                                 100 g/ha  75%                                                                  50 g/ha  75%                                          100 g/ha    135        400 g/ha  63%                                                                 200 g/ha  63%                                                                 100 g/ha  63%                                                                  50 g/ha  63%                                          400 g/ha    136        400 g/ha  88%                                                                 200 g/ha  88%                                                                 100 g/ha  88%                                                                  50 g/ha  88%                                          200 g/ha    136        400 g/ha  75%                                                                 200 g/ha  75%                                                                 100 g/ha  75%                                                                  50 g/ha  75%                                          100 g/ha    136        400 g/ha  63%                                                                 200 g/ha  63%                                                                 100 g/ha  63%                                                                  50 g/ha  63%                                          400 g/ha    140        400 g/ha  63%                                                                 200 g/ha  63%                                                                 100 g/ha  38%                                                                  50 g/ha  25%                                          200 g/ha    140        400 g/ha  63%                                                                 200 g/ha  63%                                                                 100 g/ha  63%                                                                  50 g/ha  63%                                          100 g/ha    140        400 g/ha  38%                                                                 200 g/ha  50%                                                                 100 g/ha  50%                                                                  50 g/ha  38%                                          400 g/ha    143        400 g/ha  63%                                                                 200 g/ha  63%                                                                 100 g/ha  50%                                                                  50 g/ha  38%                                          200 g/ha    143        400 g/ha  75%                                                                 200 g/ha  63%                                                                 100 g/ha  63%                                                                  50 g/ha  38%                                          100 g/ha    143        400 g/ha  38%                                                                 200 g/ha  50%                                                                 100 g/ha  50%                                                                  50 g/ha  50%                                          400 g/ha    144        400 g/ha  38%                                                                 200 g/ha  25%                                                                 100 g/ha  38%                                                                  50 g/ha  38%                                          200 g/ha    144        400 g/ha  63%                                                                 200 g/ha  63%                                                                 100 g/ha  63%                                                                  50 g/ha  63%                                          100 g/ha    144        400 g/ha  38%                                                                 200 g/ha  50%                                                                 100 g/ha  50%                                                                  50 g/ha  50%                                          400 g/ha    149        400 g/ha  50%                                                                 200 g/ha  38%                                                                 100 g/ha  38%                                                                  50 g/ha  25%                                          200 g/ha    149        400 g/ha  63%                                                                 200 g/ha  63%                                                                 100 g/ha  63%                                                                  50 g/ha  38%                                          100 g/ha    149        400 g/ha  50%                                                                 200 g/ha  38%                                                                 100 g/ha  38%                                                                  50 g/ha  25%                                          400 g/ha    152        400 g/ha  75%                                                                 200 g/ha  75%                                                                 100 g/ha  75%                                                                  50 g/ha  50%                                          200 g/ha    152        400 g/ha  75%                                                                 200 g/ha  75%                                                                 100 g/ha  75%                                                                  50 g/ha  63%                                          100 g/ha    152        400 g/ha  63%                                                                 200 g/ha  63%                                                                 100 g/ha  63%                                                                  50 g/ha  50%                                          400 g/ha    160        400 g/ha  63%                                                                 200 g/ha  75%                                                                 100 g/ha  75%                                                                  50 g/ha  63%                                          200 g/ha    160        400 g/ha  75%                                                                 200 g/ha  75%                                                                 100 g/ha  75%                                                                  50 g/ha  63%                                          100 g/ha    160        400 g/ha  50%                                                                 200 g/ha  50%                                                                 100 g/ha  50%                                                                  50 g/ha  50%                                          ______________________________________                                    

We claim:
 1. A method for protecting useful crops from the phytotoxicactivity of a herbicide applied to the crops or their environs in whichthe herbicide is a phenyoxypropionic acid of the formula: ##STR33## inwhich G is ##STR34## in which Hal₁ is a fluoro, chloro, bromo, iodo ortrifluoromethyl; Hal₂ is hydrogen, fluoro, chloro, bromo ortrifluoromethyl;Z is --N═ or --CH═; X is oxygen or sulfur; R₁ ' is halo,trifluormethyl, nitro, cyano, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy; and nrepresents 0, 1, 2 or 3.which comprises applying to the crops, theirenvirons, or the seeds from which the crops are grown, aherbicidally-antagonistic active amount of a1,5-diphenylpyrazole-3-carboxylic acid derivative of the formula##STR35## in which R₁ is (i) hydrogen; (ii) a plant-physiologicallyacceptable metal or ammonium cation; (iii) an unsubstituted,monosubstituted or polysubstituted alkyl group of 1 to 18 carbon atomsor cycloalkyl group of 3 to 18 carbon atoms in which the substituentsare selected from the group consisting of alkenyl of 2 to 8 carbonatoms, alkynyl of 2 to 8 carbon atoms, cycloalkenyl of 3 to 8 carbonatoms, halo, nitro, cyano, alkoxy of 1 to 4 carbon atoms, alkoxycarbonylof 1 to 4 carbon atoms, alkylcarbonyl of 1 to 4 carbon atoms, carbamoyl,dialkylcarbamoyl in which each alkyl group has 1 to 4 carbon atoms,amino, alkylamino of 1 to 4 carbon atoms, and dialkylamino in which eachalkyl group has 1 to 4 carbon atoms; (iv) the group -U in which U isunsubstituted, monosubstituted or polysubstituted phenyl or naphthyl inwhich the substituents are selected from the group consisting of ofhalo, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms,alkythio of 1 to 4 carbon atoms, alkylsulfinyl of 1 to 4 carbon atoms,alkylsulfonyl of 1 to 4 carbon atoms, haloalkyl of 1 to 4 carbon atoms,haloalkoxy of 1 to 4 carbon atoms, cyano, nitro, carboxy, alkoxycarbonylof 1 to 4 carbon atoms, alkylcarbonyl of 1 to 4 carbon atoms, carbamoyl,alkylcarbamoyl of 1 to 4 carbon atoms, dialkylcarbamoyl wherein eachalkyl group has 1 to 4 carbon atoms, sulfamoyl, alkylsulfamoyl of 1 to 4carbon atoms, dialkylsulfamoyl wherein each alkyl group has 1 to 4carbon atoms, pyrrolidino, piperidino, pyrrolidinocarbonyl,piperidcinocarbonyl, and morpholinocarbonyl; or (v) the group -EU inwhich U is as herein defined and E is alkylene of 1 to 4 carbon atoms,alkenylene of 2 to 4 carbon atoms, or alkynylene of 2 to 4 carbonatoms;R_(a) is hydrogen, halo, alkyl of 1 to 5 carbon atoms, haloalkylof 1 to 5 carbon atoms, alkenyl of 2 to 5 carbon atoms, alkynyl of 2 to5 carbon atoms, or cyano; R_(b) is halo, alkyl of 1 to 5 carbon atoms,haloalkyl of 1 to 5 carbon atoms, alkenyl of 2 to 5 carbon atoms,alkynyl of 2 to 5 carbon atoms, or cyano; and each n, independently ofthe other, has a value of 0 to 3 with the proviso that when Ra ishydrogen, R₁ is hydrogen or ethyl, and R6 is methyl or halo, R6 is inthe ortho position.
 2. A method for the selective control of weeds incrops of useful plants, characterised in that the crops or the areas inwhich they are grown are treateda) with a herbicidally effective amountof a herbicide of the formula ##STR36## in which T is methoxy, ethoxy,propoxy, isopropoxy, butoxy, dimethylaminoethoxy, propargyloxy,1-cyano-1-methylethoxy, methylcarbonylmethylthio,1-ethoxycarbonylethoxy, butoxycarbony, acetoximoxy,methylethylketoximoxy, or cyclohexanoximoxy, and b) either at the sameor a different ime with a herbicidally-antagonistic effective amount ofa 1,5-diphenylpyrazole-3-carboxylic acid derivative of the formula:##STR37## in which R₁ is (i) hydrogen;(ii) a plant-physiologicallyacceptable metal or ammonium cation; (iii) an unsubstituted,monosubstituted or polysubstituted alkyl group of 1 to 18 carbon atomsor cycloalkyl group of 3 to 18 carbon atoms in which the substituentsare selected from the group consisting of alkenyl of 2 to 8 carbonatoms, alkynyl of 2 to 8 carbon atoms, cycloalkenyl of 3 to 8 carbonatoms, halo, nitro, cyano, alkoxy of 1 to 4 carbon atoms, alkoxycarbonylof 1 to 4 carbon atoms, alkylcarbonyl of 1 to 4 carbon atoms, carbamoyl,dialkylcarbamoyl in which each alkyl group has 1 to 4 carbon atoms,amino, alkylamino of 1 to 4 carbon atoms, and dialkylamino in which eachalkyl group has 1 to 4 carbon atoms;(iv) the group -U in which U isunsubstituted, monosubstituted or polysubstituted phenyl or naphthyl inwhich the substituents are selected from the group consisting of halo,alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkythio of1 to 4 carbon atoms, alkylsulfinyl of 1 to 4 carbon atoms, alkylsulfonylof 1 to 4 carbon atoms, haloalkyl of 1 to 4 carbon atoms, haloalkoxy of1 to 4 carbon atoms, cyano, nitro, carboxy, alkoxycarbonyl of 1 to 4carbon atoms, alkylcarbonyl of 1 to 4 carbon atoms, carbamoyl,alkylcarbamoyl of 1 to 4 carbon atoms, dialkylcarbamoyl wherein eachalkyl group has 1 to 4 carbon atoms, sulfamoyl, alkylsulfamoyl of 1 to 4carbon atoms, dialkylsulfamoyl wherein each alkyl group has 1 to 4carbon atoms, pyrrolidino, piperidino, pyrrolidinocarbonyl,piperidcinocarbonyl, and morpholinocarbonyl; or (v) the group -EU inwhich U is as herein defined and E is alkylene of 1 to 4 carbon atoms,alkenylene of 2 to 4 carbon atoms, or alkynylene of 2 to 4 carbon atoms;R_(a) is hydrogen, halo, alkyl of 1 to 5 carbon atoms, haloalkyl of 1 to5 carbon atoms, alkenyl of 2 to 5 carbon atoms, alkynyl of 2 to 5 carbonatoms, or cyano; R_(b) is halo, alkyl of 1 to 5 carbon atoms, haloalkylof 1 to 5 carbon atoms, alkenyl of 2 to 5 carbon atoms, alkynyl of 2 to5 carbon atoms, or cyano; and each n, independently of the other, has avalue of 0 to 3 with the proviso that when Ra is hydrogen, R₁ ishydrogen or ethyl, and R6 is methyl or halo, R6 is in the orthoposition.
 3. The method according to claim 2 wherein in said1,5-diphenylpyrazole-3-carboxylic acid derivative, R₁ is alkyl of 1 to18 carbon atoms, which is unsubstituted, monosubstituted orpolysubstituted with alkenyl of 2 to 6 carbon atoms, alkynyl of 2 to 8carbon atoms, halo, nitro, cyano, or alkoxy of 1 to 4 carbon atoms. 4.The method according to claim 2 wherein in said1,5-diphenylpyrazole-3-carboxylic acid derivative, R₁ is aplant-physiologically acceptable metal or ammonium cation.
 5. The methodaccording to claim 2 wherein in said 1,5-diphenylpyrazole-3-carboxylicacid derivativeR₁ is alkyl of 1 to 18 carbon atoms, which isunsubstituted, monosubstituted or polysubstituted with alkenyl of 2 to 8carbon atoms, alkynyl of 2 to 8 carbon atoms, halo, nitro, cyano, oralkoxy of 1 to 4 carbon atoms; R_(a) is hydrogen, halo, or alkoxy of 1to 4 carbon atoms; R_(b) is halo, alkyl of 1 to 4 carbon atoms, alkoxyof 1 to 4 carbon atoms, or nitro; and n is 0 or
 1. 6. The method ofclaim 2 wherein said 1,5-diphenylpyrazole-3-carboxylic acid is1-(2-chlorophenyl)-3-methoxycarbonyl-5-phenylpyrazole.
 7. The method ofclaim 2 wherein said 1,5-diphenylpyrazole-3-carboxylic acid is1-(2,4-chlorophenyl)-3-methoxycarbonyl-5-phenylpyrazole.
 8. The methodof claim 2 wherein said 1,5-diphenylpyrazole-3-carboxylic acid is1-(2-chlorophenyl)-3-methoxycarbonyl-5-(2-fluorophenyl)pyrazole.
 9. Themethod according to claim 2 wherein said herbicide is propargyl2-[4-(3-fluoro-5-chloropyridin-2-yloxy) phenoxy]propionate.
 10. Themethod according to claim 2 wherein said herbicide is methyl2-[4-(3-fluoro-5-chloropyridin-2yloxy) phenyoxy]propionate.